DE1219152B - Process for the production of azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

C09b

German class: 22a-l

1 219 152
J19902IVc / 22a
May 12, 1961
June 16, 1966

The invention relates to a process for the preparation of new azo dyes of the trichloropyrimidine series which as reactive dyes for textile materials that contain active hydrogen, for example textile fibers natural and regenerated cellulose, made of polyamide material and of animal origin, are valuable. It has been found that new azo dyes are obtained which are in the form of the free acid of the formula

SO ₃ H

R- ( VcH =

SO ₃ H

-N = N-X-N-T

wherein R is a halogen atom, a nitro group, an acylamido group, a substituted amino group, except monoalkylamino, or an optionally substituted by sulfonic acid r, 2 ', 4,5-naphthatriazolyl group, X is a phenylene or naphthylene radical which is optionally substituted except by amino or monoalkylamino, Y denotes hydrogen or an alkyl radical and T denotes a trihalopyrimidyl radical if Process for the production of azo dyes

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr
and Dipl.-Ing. S. Staeger, patent attorneys,
Munich 5, Müller str. 31

Named as inventor:

Herbert Francis Andrew,

Donald Buckley, Blackley, Manchester

(Great Britain)

Claimed piracy:
Great Britain dated May 13, 1960 (16 938),
dated April 28, 1961

essentially equimolecular proportions of a tetrahalopyrimidine and an amino dye which, in the form of the free acid, has the formula

R— ζ

SO ₃ H

N-CH =

SO ₃ H

N = N-X-NHY

has, in which R, X and Y have the meanings given above, are reacted with one another.

With essentially equimolecular proportions such relative proportions are meant that at most 20 percent by weight of one or the other reactant in excess of the molecular amount, which is equivalent to the amount used by the other reactant are present.

As examples of halogen atoms which may be represented by R, there may be mentioned chlorine and Bromine, acetamido and benzoylamido groups may be mentioned as examples of acylamido groups, and as examples of substituted amino groups there may be mentioned dialkylamino groups, such as the dimethylamino group, Diaralkylamino groups, such as the dibenzylamino group, and arylamino groups, such as phenylamino and p-nitrophenylamino groups.

As examples of alkyl radicals represented by Y, there may be mentioned: methyl, ethyl, butyl, hexyl and octyl radicals.
Examples of substituents that may be present in a phenylene or naphthylene radical represented by X include halogen such as chlorine, and also nitro, SuKo-, carboxy, alkyl such as methyl, alkoxy such as methoxy and ethoxy, Hydroxy, acylamido, such as acetamido and benzoylamido, dialkylamino such as dimethylamino and diethylamino, diaralkylamino such as dibenzylamino or substituted dibenzylamino, and atrylamino and phenylamino or substituted phenylamino groups.

The exact configuration of the trihalopyrimidyl radical represented by T is not certain known. Probably this remainder is one

609 579/365

3 4

4,5,6-trihalopyrimid-2-yl radical, but it is also and cellulosic textile materials, e.g. B. cotton, linen

it is possible that a 2,5,6-trihalopyrimidr4-ykest and viscose rayon can be used,

is. As examples of halogen atoms which are present in those colorants produced according to the invention

Trihalogenpyrimidyl radicals represented by T, in which R denotes a nitro group, are

may be present, chlorine and bromine are particularly valuable, since the

thinks. color shades obtained from textile materials, good bleaching

Examples of tetrahalopyrimidines are said to have resistance and little or no

mentioned tetrachloropyrimidine, tetrabromopyrimidine and show decrease in lightfastness when the stained

2,4,6-trichloro-5-bromopyrimidine. . · Textile material treatments to improve it

The aminoazover- io used as starting materials is subjected to crease resistance, for example im-

bonds of the above formula can be obtained impregnation with urea-formaldehyde resin,

by coupling a diazotized amine of the formula In the following examples, parts refer to

Weight.

SO _a H SO _S H

_ig example

² 5.5 parts of the disodium salt obtained by coupling diazotized 4-amino-4'-nitrostilbene-2,2'-disulfonworin R has the meaning given above, with an acid with aniline aminoazo compound arylamine or alkylarylamine, z. B. aniline (in the form of ao are dissolved in 200 parts of water and a solution of ω-methanesulfonate), m-toluidine, 2-methoxy solution of 2.7 parts of tetrachloropyrimidine in 30 parts of 5-methylaniline, l-naphthylamine-6- sulfonic acid, o-ani-dioxane given. The mixture is stirred for 4 hours at sidin, 2,5-dimethoxyaniline, m-anisidine, 1-naphthyl 55 to 6O ⁰ C, and 2N sodium carbonate amine-sulfonic acid 7-, "naphthylamine, monomethyl is added in intervals, to keep the solution neutral aniline, monoethylaniline, monobutylaniline anthranil-25. The mixture is then acid (in the form of its ω-methanesulfonate) and 1-ami- of unreacted tetrachloropyrimidine with Wasno-8-hydroxynaphthalene-3,6-disulfonic acid to remove. Steam distilled and cooled: 25 parts of sodium ais special examples of amines of the above chloride are added, and the precipitated color formula may be mentioned 4'-chloro-4-aminostilbene-2,2'-di- substance is filtered off and dried,
sulfonic acid, 4'-bromo-4-aminostilbene-2,2'-disulfone-30 If the dye is used in conjunction with an acidic, 4'-nitro-4-aminostilbene-2,2'-disulfonic acid, acid-binding agent on cellulose textile materials 4 '-Acetamido - 4 - aminostilbene - 2,2' - disulfonic acid, applies, it delivers orange tones with very good 4'-benzolyamido - 4 - aminostilbene - 2,2'-disulfonic acid, light and wash fastness.
4'-dimethylamino-4-aminostilbene-2,2'-disulfonic acid,

4'-anilino-4-aminostilbene-2,2'-disulfonic acid or 35 Example 2
4'-dibenzylamino-4-aminostilbene-2,2'-disulfonic acid

and 4 '- (5 "' - Sutfo-l"', 2 "', 4", 5 "-naphthatriazol-2" -yl) - 5.62 parts of the disodium salt of the 4-aminostilbene-2,2 'by coupling -disulfonic acid, 4 '- (4'"- SUh ⁵ O-I '", of diazotized 4-amino-4'-nitrostilbene-2,2-disulfon-2 "', 4", 5 "-naphthatriazole-2" -yl) -4-aminostilbene-2,2'-diacid obtained with N-methylaniline aminoazoversulfonic acid, 4 '- (5'", 7 '" - DisuhO-1'", 2 '", 4 ", 5" -naph - 40 bond are dissolved in 200 parts of water and thatriazol-2 "-yl) -4-aminostilbene-2,2'-disulfonic acid, a solution of 2.7 parts of tetrachloropyrimidine in 4 '- (3'", 6 '" , 8 '"- TrisuhO-1'", 2 '", 4", 5 "-naphthatriazole- 30 parts of dioxane are added. The mixture is 4 Stun-2" - yl) -4-aminostilben-2,2'- disulfonic acid. The stirred at 55 to 60 ° C, and 2N sodium carbonate-The process according to the invention can expediently solution is added at intervals in order to keep the solution usually neutral in an aqueous medium, for example 45. The mixture is then distilled with water-water or a mixture of water and a steam to remove unconfined tetrachloro-water-soluble organic solvent such as acetone pyrimidine and cooled. 25 parts sodium or dioxane, at a temperature between 20 and chloride are added and the precipitated dye 100 C, preferably between 50 and 6O ⁰ C, transit ° is filtered off and dried,
be guided. Optionally, an acidic binding agent can be used. B. sodium carbonate or sodium binding agents on cellulosic textile materials on bicarbonate, are added. Unreacted halo is brought, it delivers orange tones with very gene pyrimidine can then be removed if necessary good light and wash fastness,
the, z. B. by steam distillation, and the If instead of the 2.7 parts of tetrachloropyrimidine can then advantageously be salted out 55 midin in this example 5.2 parts of tetrabromopyrimidine and filtered off. In general, it is used in advance if a similar dye is obtained,
moved the new dyes from the medium in

which they were formed ° at a pH of 6 to 8 Example3
to isolate and the dye pastes obtained

dry, preferably in the presence of buffer with 60 17.5 parts of the disodium salt of l-amino-8-naph-

Teln, which are used to maintain a pH value of thol-3,6-disulfonic acid in 100 parts of water

about 6.5 are suitable. Examples of such buffers- dissolved, and the pH is adjusted by adding sodium-

Medium mixtures of sodium dihydrogen phosphate are set to 8. The solution becomes one

phate and disodium hydrogen phosphate or from a solution of 10.9 parts of tetrachloropyrimidine in 75 parts

sodium hydrogen phosphate and potassium dihydrogen 65 len dioxane, and the mixture is 1 hour

phosphate. stirred at 40 to 45 ⁰ C. The pH is adjusted by adding

The new dyes according to the invention can be adjusted from 2N sodium carbonate solution to 7, and

for dyeing silk, wool, regenerated protein. heating is continued until the pH is reached without further

Addition of sodium carbonate remains at 7. The solution is adjusted to pH 9.5 and immediately cooled to 5 ° C.

A solution of the diazo compound obtained from 22.2 parts of the disodium salt of 4-amino-4'-nitrostilbene-2,2'-disulfonic acid is added to the coupling component solution thus obtained. The mixture is stirred until completion of the coupling below 1O ⁰ C, the pH between 8 and 9 is held, and the product is precipitated by addition of sodium chloride, filtered off and dried.

If you use the dye in conjunction with a treatment with an acid-binding agent When applying cellulose textile materials, it delivers violet, lightfast and washfast tones.

Example 4

8.9 parts of the tetrasodium salt of 4 '- (5'", 7 '" - disulfo-1 "', 2 '", 4 ", 5" - naphthatriazol - 2 "- yl) - 4 diazotized by coupling of one mole portion - aminostilben-2,2'-disulfonic acid with a molar proportion of N-methylaniline aminoazo compound obtained is dissolved in 250 parts of water, the solution is added to a solution of 2.7 parts of tetrachloropyrimidine in 20 parts of dioxane, and the mixture is 4 hours at 6O ⁰ C. The mixture is kept neutral by adding 2N sodium carbonate solution. The mixture is cooled and 25 parts of sodium chloride are added. The dye is filtered off, suspended in acetone, filtered again and dried. The product has the formula:

SO ₃ N

NaO ₃ S

CH = CH

SO ₃ Na

N = N

CH ₃

N-T

NaO.S

where T is a trichloropyrimidinyl radical.

Using the dye in conjunction with an acid binding agent on cellulosic fabrics applies, it delivers orange-colored, washable and lightfast tones.

The following table gives the tones of dyes obtained by coupling the in the first column listed diazotized amines with the coupling components listed in the second column and reacting the aminoazo compounds thus obtained with a stoichiometrically equivalent one Amount of tetrachloropyrimidine obtained under the conditions described in Examples 1 and 2 became.

Using the dyes in conjunction with an acid binding agent on cellulosic textile materials applies, they deliver all washable and lightfast colors.

example Amine Coupling component hue 5 4-amino-4'-acetamidostilbene-2,2-disulfonic acid N-methylaniline Reddish yellow 6th 4-amino-4'-chlorostilbene-2,2'-disulfonic acid N-methylaniline Reddish yellow 7th 4-amino-4'-bromostilbene-2,2'-disulfonic acid aniline Reddish yellow 8th 4-amino-4'-acetamidostilbene-2,2'-disulfonic acid 2,5-dimethoxyaniline orange 9 4-amino-4'-acetamidostilbene-2,2'-disulfonic acid 2-methoxy-5-methylaneum orange 10 4-amino-4'-nitrostilbene-2,2'-disulfonic acid m-aminoacetanilide orange 11 4-amino-4'-nitrostilbene-2,2'-disulfonic acid m-toluidine Reddish yellow 12th 4-Amino-4'-benzoylaminostilbene-2,2'-disulfonic acid N-ethylaniline orange 13th 4-amino-4'-dimethyl-aminostilbene-2,2'-disulfonic acid N-methylaniline orange

Claims (1)

Claim: Process for the preparation of azo dyes, characterized in that one essentially equimolecular proportions of a tetrahalopyrimidine and an aminoazo dye, which in the form of its free acid of the formula SO, H CH = CH SO ₃ H N = N-X-N-T corresponds to where R is a halogen atom, a nitro group, an acylamido group, a substituted one Amino group, except monoalkylamino, or an optionally substituted by sulfonic acid l ', 2', 4,5-naphthatriazolyl group, X an optionally, but not by amino or mono- alkylamino, substituted phenylene or naphthylene radical and Y is hydrogen or an alkyl radical means, with the formation of an azo dye, which is in the form of the free acid of the formula SO ₃ H SOoH CH = CH = N-X-NHY corresponds to where R _5, X and Y have the meanings given above and T is a trihalopyrimidyl radical, preferably a trichloropyrimidyl radical, is reacted with one another. When the application was announced, a coloring table with explanations was laid out. 609 579/365 6.66 © Bundesdruckerei Berlin